CN1919837A - m-benzenedicarbonyl thioureas derivative, preparation and application thereof as fluorinion identification receptor - Google Patents
m-benzenedicarbonyl thioureas derivative, preparation and application thereof as fluorinion identification receptor Download PDFInfo
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- CN1919837A CN1919837A CN 200610104536 CN200610104536A CN1919837A CN 1919837 A CN1919837 A CN 1919837A CN 200610104536 CN200610104536 CN 200610104536 CN 200610104536 A CN200610104536 A CN 200610104536A CN 1919837 A CN1919837 A CN 1919837A
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Abstract
The invention discloses an acceptor isophthalonacyl sulfourea derivative 3a, 3b and 3c and phase-transfering solvent-free grinding preparing method, which comprises the following steps: adding isophthalonacyl and ammonium sulfocyanate in the mortar according to certain rate; grinding intervally for 5-7h under indoor temperature to obtain isophthalonacyl isosulfocyanate; adding substituted arylamine to grind intervally under indoor temperature for 6-48h; obtaining yellow or light yellow sediment; filtering; washing; recrystallizing through DMF-C2H5OH-H2O.
Description
Technical field
The present invention relates to the solvent-free grinding process for preparing of phase-transfer catalysis of a class m-benzenedicarbonyl thioureas derivative and this analog derivative, also relate to of the application of this analog derivative simultaneously as the fluorion identification receptor.
Background technology
Intermolecular interaction of Subjective and Objective and mutually identification particularly have the interaction between the Subjective and Objective of optical information response function, are one of advanced subject of present supramolecular chemistry research field.Molecular recognition is main object selective binding and the process that produces certain specific function, is the basis of the necessary ways and the research assembly function of assembling higher structure.Negatively charged ion plays an important role in the metabolic process of organism, and it is finished under corresponding protein-bonded control and identification in the transmission inside and outside the cytolemma.In the potential application aspect biology, clinical medicine, the environmental monitoring, anionic identification is become in the supramolecular chemistry one by the problem of extensive concern based on it, especially bore hole is discerned certain negatively charged ion and is caused the great interest of people.The cation radius of its electric charge such as grade of anion ratio is big, has less electric density, thereby electrostatic interaction in anionic recognition process relatively positively charged ion be secondary cause, particularly for the electric neutrality acceptor, discerning anionic impellent mainly is hydrogen bond action.
Thiourea derivative is not only the important compound with broad practice of a class, and owing to contain two relative tart amide nitrogen hydrogen protons, in the molecular recognition process, can form the multiple hydrogen bonding effect, therefore in supramolecular chemistry, receive much attention with the object negatively charged ion.Position substituting thioureido acceptor between phenyl ring, its space structure is similar to " pliers ", and such pincers receptor can form the quadruple hydrogen bond with negatively charged ion, and the stability constant of anionic complex is greater than corresponding linear acceptor.
The solvent-free polishing of phase-transfer catalysis is to be phase-transfer catalyst with polyoxyethylene glycol-400 (PEG-400), the griding reaction under condition of no solvent.This synthetic method has cleaning, efficient, easy and simple to handle, and aftertreatment is simple, and productive rate is higher, and energy consumption is low, pollutes plurality of advantages such as few.Though conventional solvent method equipment is simple, easy and simple to handle, there are solvent evaporates waste, defective such as inflammable in the reaction, easily cause environmental pollution and potential safety hazard.Therefore, utilize solvent-free polishing synthesizing thiourea derivative, avoided the use of a large amount of solvents, have realistic meaning solving environmental pollution.
Ultraviolet-visible (UV-Vis),
1The HNMR spectrography is widely used in the system of the spectrum change that the inclusion coordination reaction causes, demonstrates fully the hydrogen bond action essence between acceptor molecule and negatively charged ion, is a kind of comparatively simple, fast mensuration means for the stability constant of measuring super molecular complex.
Summary of the invention
The purpose of this invention is to provide a class m-benzenedicarbonyl thioureas derivative;
Another object of the present invention provides a kind of method of utilizing the solvent-free polishing of mortar to prepare above-mentioned m-benzenedicarbonyl thioureas derivative;
A further object of the invention: promptly m-benzenedicarbonyl thioureas derivative is as the application of fluorion identification receptor.
One, m-benzenedicarbonyl thioureas derivative of the present invention:
Its molecular structural formula is shown below:
R=NO wherein
2, be m-benzenedicarbonyl thioureas derivative 3a;
R=H is m-benzenedicarbonyl thioureas derivative 3b;
R=OC
2H
5, be m-benzenedicarbonyl thioureas derivative 3c.
M-benzenedicarbonyl thioureas derivative acceptor of the present invention determines that by ultimate analysis, infrared absorption spectrum and proton nmr spectra the result is as follows:
M-benzenedicarbonyl thioureas derivative 3a: yellow solid, m.p.201-202 ℃; IR (KBr): 3179,2998 (N-H); 1727 (C=O); 1516 (C=C); 1242,1181 (C=S); 770,737 (C-N) cm
-1.
1H NMR (DMSO-d
6): δ 12.81 (s, 2H, NHCO), 11.26 (s, 2H, NHAr), 7.18-8.49 (m, 12H, ArH) .Elemental analysis:calcd for C
22H
16N
6O
6S
2: C50.38%, H3.05%, N16.03%; Found:C50.40%, H3.08%, N15.99%.
M-benzenedicarbonyl thioureas derivative 3b: faint yellow solid, m.p.197-198 ℃; IR (KBr): 3298,3223,3173,3033 (N-H); 1700 (C=O); 1599,1526 (C=C); 1348,1246,1145 (C=S) cm
-1.
1H NMR (DMSO-d
6): δ 12.56 (s, 2H, NHCO), 11.60 (s, 2H, NHAr), 7.28-8.58 (m, 14H, ArH) .Elemental analysis:calcd for C
22H
18N
4O
2S
2: C60.83%, H4.15%, N12.90%; Found:C60.86%, H4.12%, N12.86%.
M-benzenedicarbonyl thioureas derivative 3c: faint yellow solid, m.p.205-206 ℃; IR (KBr): 3242,3036 (N-H); 1680 (C=O); 1601,1549 (C=C); 1231,1150 (C=S) cm
-1.
1H NMR (DMSO-d
6): δ 12.98 (s, 2H, NHCO), 11.33 (s, 2H, NHAr), 7.24-8.71 (m, 12H, ArH), 4.18 (t, 4H, CH
2), 1.41 (m, 6H, CH
3) .Elemental analysis:calcd forC
26H
26N
4O
4S
2: C59.77%, H4.98%, N10.73%; Found:C59.73%, H4.96%, N10.78%.
Two, m-benzenedicarbonyl thioureas derivative of the present invention (preparation method of 3a～3c):
Be that m-phthaloyl chloride and the ammonium thiocyanate mol ratio with 1: 2.5～1: 3 is joined in the mortar, under the condition of phase-transfer catalyst, griding reaction 5～7 hours intermittently under room temperature obtains the isophthaloyl lsothiocyanates; The substituted aromatic amines that adds 2～2.5 times of m-phthaloyl chloride amount of substances again, griding reaction 6～48 hours intermittently under room temperature obtains yellow or flaxen precipitation; Filter, wash, and with the organic solvent recrystallization promptly.
Its synthetic route is as follows:
R=NO wherein
2, be m-benzenedicarbonyl thioureas derivative 3a;
R=H is m-benzenedicarbonyl thioureas derivative 3b;
R=OC
2H
5, be m-benzenedicarbonyl thioureas derivative 3c.
The phase-transfer catalyst that the present invention adopts is a polyoxyethylene glycol-400, and its add-on is 2～4% of an ammonium thiocyanate amount of substance.
Described organic solvent is DMF (dimethyl formamide)-C
2H
5OH-H
2O mixed solvent, wherein DMF: C
2H
5OH: H
2The mol ratio of O is 1: 0.8: 0.4～1: 1.2: 0.6.
The technology that the present invention prepares the m-benzenedicarbonyl thioureas derivative acceptor is simple, productive rate height, generally (3a productive rate: 72.4% between 70～88%; 3b productive rate: 87.5%; 3c productive rate: 84.2%).
Three, m-benzenedicarbonyl thioureas derivative of the present invention is as the application of fluorion identification receptor
M-benzenedicarbonyl thioureas derivative of the present invention is determined as the ultraviolet-visible absorption spectra of DMSO solution that can be by survey itself and anionic 4-butyl ammonium to the recognition performance of the selectivity identification receptor of fluorion:
Pipette the DMSO solution (2 * 10 of 1mL acceptor 3a, 3b, 3c respectively
-4Mol * L
-1) in a series of 10mL colorimetric cylinders, solution is all colourless.Add 1mLF respectively
-, Cl
-, Br
-, I
-DMSO solution (0.01mol * the L of anionic 4-butyl ammonium
-1), be diluted to scale with DMSO, make the concentration of acceptor be 2 * 10
-5Mol * L
-1, making various anion concentrations is 50 times of acceptor density, surveys its uv-visible absorption spectras (DMSO makes reference) in 25 ℃ immediately after mixing.
When in the DMSO of acceptor molecule 3a, 3b, 3c solution, adding Cl
-, Br
-, I
-The DMSO solution of 4-butyl ammonium the time, the absorption spectrum of solution has no significant change, and this type of acceptor molecule is described to the not obviously effect of these several negatively charged ion, and adds F
-The time, absorption spectrum all changes, and the solution colour of acceptor 3a has considerable change, illustrates that this type of acceptor molecule is to F
-Selectivity is preferably arranged, and 3a has the bore hole identification selection, as Fig. 1 (is example with acceptor molecule 3a).
When not adding negatively charged ion, because intramolecular charge shifts, acceptor molecule 3a, 3b, 3c be respectively at 270nm, 266nm, and there is maximum absorption band at the 272nm place.Add object negatively charged ion F respectively
-Shi Junneng causes the noticeable change of acceptor molecule absorption spectrum, and the 3a solution colour is from the colourless yellow that changes at once, and with the anion concentration increase, solution colour is deepened gradually.
Pipette the DMSO solution (2 * 10 of 2mL acceptor 3a, 3b, 3c respectively
-5Mol * L
-1) in the 1cm quartz colorimetric utensil, add the F of different volumes respectively
-The DMSO solution (0.1mol * L of 4-butyl ammonium
-1), survey its uv-visible absorption spectra (DMSO makes reference) in 25 ℃.
With acceptor molecule 3a is example, when adding F
-The time, the absorbancy at 270nm place is with F
-Concentration increases and reduces gradually, occurs one group of new absorption peak simultaneously at the 417nm place, and this peak is the absorption peak that forms new title complex between acceptor molecule and the negatively charged ion, and peak value is with F
-Concentration increases corresponding increase.Show acceptor molecule and the anionic degree that has promoted that further intramolecular charge shifts that combines.Can be observed simultaneously at the 362nm place has an isobestic point, illustrates that stable title complex generates.See Fig. 2.
Acceptor 3b and 3c are adding F respectively
-The time its absorption spectrum change and be similar to 3a.In acceptor molecule 3b, add F
-The time 266nm place absorption peak increase with anion concentration and reduce gradually.Simultaneously at one group of new absorption peak of 321nm place appearance, and can obviously observe an isobestic point is arranged at the 283nm place.In acceptor molecule 3c, add F
-The time 272nm place absorption peak increase with anion concentration and reduce gradually.Simultaneously at one group of new absorption peak of 325nm place appearance, and can obviously observe an isobestic point is arranged at the 294nm place.Calculate through the least square curve fit program, can draw acceptor molecule 3a, 3b, 3c and F
-Coordination constant K s and coefficient R (seeing Table 1), and be example with acceptor molecule 3a, make itself and F
-Fitting of a curve figure (see figure 3).
Table 1 acceptor molecule 3a, 3b, 3c and F
-Coordination constant K s and coefficient R
| 3a | 3b | 3c | |
| Ks(mol/L) -1 R | 1.94×10 5 0.9981 | 7.2×10 4 0.9989 | 6.5×10 4 0.9905 |
The present invention is by the deducibility of uv-visible absorption spectra method, and the cis-structure of such acceptor molecule is more stable, because acceptor molecule and negatively charged ion form 1: 1 stable complex, its binding pattern can be presumed as follows again.
Hydrogen bond action essence between m-benzenedicarbonyl thioureas derivative acceptor molecule of the present invention and negatively charged ion can be passed through
1The HNMR titration experiments is further determined:
Get 3 nuclear-magnetism pipes, add the DMSO-d of acceptor 3a, 3b, 3c respectively
6Solution, concentration is 1.0 * 10
-2Mol * L
-1, survey its proton nmr spectra, in the nuclear-magnetism pipe of 3a, 3b, 3c, add isopyknic object F then respectively
-, Cl
-, Br
-, I
-4-butyl ammonium DMSO-d
6Solution (1.0 * 10
-2Mol * L
-1), measure its proton nmr spectra respectively in 25 ℃.With acceptor molecule 3c is example, with DMSO-d
6Be solvent, the NH chemical shift of proton of acceptor molecule 3c is δ 12.98 and δ 11.33.As the F that adds a times
-The DMSO-d of 4-butyl ammonium
6During solution, the NH proton peak almost completely disappears.Its
1HNMR titration spectrogram is seen Fig. 4.Accordingly, at F
-The proton nmr spectra of acceptor molecule 3a, 3b also has similar variation when existing.And the Cl of acceptor 3a, 3b, 3c
-, Br
-, I
-The proton nmr spectra of solution is no change but.
The Anion Recognition experimental result shows:
1, m-benzenedicarbonyl thioureas derivative acceptor molecule of the present invention has high identification selection to fluorion in halide anion.
2, acceptor molecule 3a of the present invention changes obviously solution colour in the fluorion recognition process, has realized the purpose of bore hole identification, and acceptor molecule 3a becomes more effectively good fluorion identification receptor.
3, the present invention calculates through the least square curve fit program, and these three kinds of acceptor molecules are identical with substituting group position on the phenyl ring, but the sub-ability of powering is different to F
-Recognition reaction present certain rules.Be that acceptor molecule is to F
-Recognition reaction be 3a＞3b＞3c.Because when substituting group on the phenyl ring is electrophilic nitro, form the bonding force maximum of hydrogen bond, i.e. equilibrium constant maximum, this is because the electron-withdrawing power of nitro and its bigger electronegativity, makes that the acidity of thiocarbamide NH proton strengthens easier formation hydrogen bond in the molecule.When substituting group is oxyethyl group, because oxyethyl group group volume is bigger, there is mutual repulsion effect, make that the spatial volume between two thiourea groups increases, so the isophthaloyl thiocarbamide and the F of oxyethyl group replacement
-Form the acceptor difficulty that hydrogen bond replaces than nitro.Reach by uv-visible absorption spectra
1The HNMR titration experiments can infer that the cis-structure of such acceptor molecule is more stable, and acceptor molecule and 1: 1 stable complex of negatively charged ion formation, and its binding pattern as previously shown.
4, the present invention
1In the HNMR titration experiments, the variation of NH proton absorption peak suffices to show that the thiocarbamide NH proton of acceptor molecule has participated in the formation of hydrogen bond as anionic binding site.
Acceptor molecule of the present invention is with substituent difference on the phenyl ring, and effect presents certain rules to Anion Recognition.The acceptor 3a that is strong electron-withdrawing group replacement on the phenyl ring is to F
-The recognition reaction maximum, the acceptor 3b of unsubstituted takes second place, the acceptor 3c minimum that electron-donating group replaces.Utilize
1HNMR (nuclear-magnetism) titration experiments is for the hydrogen bond action essence between acceptor molecule and negatively charged ion provides direct foundation.
Vertical the above, be acceptor with m-benzenedicarbonyl thioureas derivative 3a, can be by visual inspection with the identification fluorion: pipette 2 * 10 of 1mL 3a acceptor respectively
-4Mol * L
-1DMSO solution adds 1mLF respectively in a series of 10mL colorimetric cylinders
-, Cl
-, Br
-, I
-0.01mol * the L of anionic 4-butyl ammonium
-1DMSO solution is diluted to scale with DMSO, and the concentration that makes the 3a acceptor is 2 * 10
-5Mol * L
-1, and various anion concentration is 50 times of the 3a acceptor density, mixes the back and observes colour-change, if solution colour becomes yellow, then is F
-Anion solutions.
With m-benzenedicarbonyl thioureas derivative 3a is acceptor, also can discern fluorion by the uv-visible absorption spectra method: pipette 2 * 10 of 1mL3a acceptor respectively
-4Mol * L
-1DMSO solution adds 1mL F respectively in a series of 10mL colorimetric cylinders
-, Cl
-, Br
-, I
-0.01mol * the L of anionic 4-butyl ammonium
-1DMSO solution is diluted to scale with DMSO, and the concentration that makes the 3a acceptor is 2 * 10
-5Mol * L
-1, and various anion concentration is 50 times of the 3a acceptor density, mixes, and surveys its uv-visible absorption spectras in 25 ℃, if find that solution at one group of new absorption peak of 417nm place appearance, then is F
-Anion solutions.
With m-benzenedicarbonyl thioureas derivative 3b is acceptor, also can discern fluorion by the uv-visible absorption spectra method: pipette 2 * 10 of 1mL3b acceptor respectively
-4Mol * L
-1DMSO solution is in a series of 10mL colorimetric cylinders; Add 1mL F respectively
-, Cl
-, Br
-, I
-0.01mol * the L of anionic 4-butyl ammonium
-1DMSO solution is diluted to scale with DMSO, and the concentration that makes acceptor 3b is 2 * 10
-5Mol * L
-1, and various anion concentration is 50 times of the 3b acceptor density, mixes, and surveys its ultraviolet-visible absorption spectra in 25 ℃, if find that solution at one group of new absorption peak of 321nm place appearance, then is F
-Anion solutions.
With m-benzenedicarbonyl thioureas derivative 3c is acceptor, also can discern fluorion by the uv-visible absorption spectra method: pipette 2 * 10 of 1mL acceptor 3c respectively
-4Mol * L
-1DMSO solution is in a series of 10mL colorimetric cylinders; Add 1mL F respectively
-, Cl
-, Br
-, I
-0.01mol * the L of anionic 4-butyl ammonium
-1DMSO solution is diluted to scale with DMSO, and the concentration that makes acceptor 3c is 2 * 10
-5Mol * L
-1, and various anion concentration is 50 times of the 3b acceptor density, mixes, and surveys its ultraviolet-visible absorption spectra in 25 ℃, finds that solution at one group of new absorption peak of 325nm place appearance, then is F
-Anion solutions.
With m-benzenedicarbonyl thioureas derivative 3a, 3b, 3c is acceptor, also can pass through proton nmr spectra (
1HNMR) identification fluorion: in the nuclear-magnetism pipe, add 1.0 * 10 of acceptor 3a or 3b or 3c
-2Mol * L
-1DMSO-d
6Solution is surveyed its proton nmr spectra, adds isopyknic object F then in the nuclear-magnetism pipe respectively
-, Cl
-, Br
-, I
-4-butyl ammonium 1.0 * 10
-2Mol * L
-1DMSO-d
6Solution is measured its proton nmr spectra respectively in 25 ℃; If the NH chemical shift of proton of acceptor molecule disappears, and then is F
-Negatively charged ion.
Beneficial effect of the present invention:
1, m-benzenedicarbonyl thioureas derivative acceptor of the present invention all has high identification selection to fluorion.
2, acceptor molecule 3a of the present invention is owing to the introducing of fluorion, and therefore solution colour can utilize its obvious color to change bore hole identification fluorion by the colourless yellow that becomes.
3, the simple synthetic method of m-benzenedicarbonyl thioureas derivative acceptor of the present invention is efficient, and environmental protection solves in the conventional solvent method solvent evaporates waste, environment and safety problem such as inflammable.
Description of drawings
Ultraviolet-the visible absorption spectra of Fig. 1 acceptor molecule 3a and halide anion
Fig. 2 is F in DMSO
-Ultraviolet-visible absorption spectra of acceptor 3a when existing
Fig. 3 acceptor molecule 3a and F
-Matched curve figure
Fig. 4 DMSO-d
6In acceptor molecule 3c and when fluorion exists
1The HNMR spectrum
The part of (1) acceptor molecule 3c wherein
1The HNMR spectrum; (2) acceptor molecule 3c when fluorion exists
1The HNMR spectrum.
Embodiment
Embodiment 1, the preparation method of m-benzenedicarbonyl thioureas derivative 3a of the present invention: be that m-phthaloyl chloride and the ammonium thiocyanate mol ratio with 1: 2.5 is joined in the mortar, the polyoxyethylene glycol-400 that adds ammonium thiocyanate amount of substance 2% again, griding reaction 5 hours intermittently under room temperature obtains the isophthaloyl lsothiocyanates; The o-Nitraniline that adds 2 times of m-phthaloyl chloride amount of substances again, griding reaction 6 hours intermittently under room temperature obtains yellow mercury oxide; Filter, wash, and use DMF-C
2H
5OH-H
2O (DMF: C wherein
2H
5OH: H
2The mol ratio of O is 1: 0.8: 0.4) the mixed solvent recrystallization promptly gets m-benzenedicarbonyl thioureas derivative 3a, and its productive rate is 72.4%.
The preparation method of embodiment 2, m-benzenedicarbonyl thioureas derivative 3b of the present invention: be that m-phthaloyl chloride and the ammonium thiocyanate mol ratio with 1: 2.8 is joined in the mortar, the polyoxyethylene glycol-400 that adds ammonium thiocyanate amount of substance 3% again, griding reaction 6 hours intermittently under room temperature obtains the isophthaloyl lsothiocyanates; The aniline that adds 2.2 times of m-phthaloyl chloride amount of substances again, griding reaction 24 hours intermittently under room temperature obtains flaxen precipitation; Filter, wash, and use DMF-C
2H
5OH-H
2O (DMF: C wherein
2H
5OH: H
2The mol ratio of O is 1: 1.0: 0.5) the mixed solvent recrystallization promptly gets m-benzenedicarbonyl thioureas derivative 3b, and its productive rate is 87.5%.
The preparation method of embodiment 3, m-benzenedicarbonyl thioureas derivative 3c of the present invention: be that m-phthaloyl chloride and the ammonium thiocyanate mol ratio with 1: 3 is joined in the mortar, the polyoxyethylene glycol-400 that adds ammonium thiocyanate amount of substance 4% again, griding reaction 7 hours intermittently under room temperature obtains the isophthaloyl lsothiocyanates; The O-ethoxyl amine that adds 2.5 times of m-phthaloyl chloride amount of substances again, griding reaction 48 hours intermittently under room temperature obtains flaxen precipitation; Filter, wash, and use DMF-C
2H
5OH-H
2O (DMF: C wherein
2H
5OH: H
2The mol ratio of O is 1: 1.2: 0.6) the mixed solvent recrystallization promptly gets m-benzenedicarbonyl thioureas derivative 3c, and its productive rate is 84.2%.
Embodiment 4: with m-benzenedicarbonyl thioureas derivative 3a is acceptor identification fluorion: pipette 2 * 10 of 1mL 3a acceptor respectively
-4Mol * L
-1DMSO solution adds 1mL F respectively in a series of 10mL colorimetric cylinders
-, Cl
-, Br
-, I
-0.01mol * the L of anionic 4-butyl ammonium
-1DMSO solution is diluted to scale with DMSO, and the concentration that makes the 3a acceptor is 2 * 10
-5Mol * L
-1, and various anion concentration is 50 times of the 3a acceptor density, mixes the back and observes colour-change, if solution colour becomes yellow, then is F
-Anion solutions.
Embodiment 5, be acceptor, by uv-visible absorption spectra method identification fluorion: pipette 2 * 10 of 1mL3a acceptor respectively with m-benzenedicarbonyl thioureas derivative 3a
-4Mol * L
-1DMSO solution adds 1mL F respectively in a series of 10mL colorimetric cylinders
-, Cl
-, Br
-, I
-0.01mol * the L of anionic 4-butyl ammonium
-1DMSO solution is diluted to scale with DMSO, and the concentration that makes the 3a acceptor is 2 * 10
-5Mol * L
-1, and various anion concentration is 50 times of the 3a acceptor density, mixes, and surveys its uv-visible absorption spectras in 25 ℃, if find that solution at one group of new absorption peak of 417nm place appearance, then is F
-Anion solutions.
Embodiment 6, be acceptor, by uv-visible absorption spectra method identification fluorion: pipette 2 * 10 of 1mL3b acceptor respectively with m-benzenedicarbonyl thioureas derivative 3b
-4Mol * L
-1DMSO solution is in a series of 10mL colorimetric cylinders; Add 1mL F respectively
-, Cl
-, Br
-, I
-0.01mol * the L of anionic 4-butyl ammonium
-1DMSO solution is diluted to scale with DMSO, and the concentration that makes acceptor 3b is 2 * 10
-5Mol * L
-1, and various anion concentration is 50 times of the 3b acceptor density, mixes, and surveys its ultraviolet-visible absorption spectra in 25 ℃, if find that solution at one group of new absorption peak of 321nm place appearance, then is F
-Anion solutions.
Embodiment 7, be acceptor with m-benzenedicarbonyl thioureas derivative 3c, also can be by uv-visible absorption spectra method identification fluorion: pipette 2 * 10 of 1mL acceptor 3c respectively
-4Mol * L
-1DMSO solution is in a series of 10mL colorimetric cylinders; Add 1mL F respectively
-, Cl
-, Br
-, I
-0.01mol * the L of anionic 4-butyl ammonium
-1DMSO solution is diluted to scale with DMSO, and the concentration that makes acceptor 3c is 2 * 10
-5Mol * L
-1, and various anion concentration is 50 times of the 3c acceptor density, mixes, and surveys its ultraviolet-visible absorption spectra in 25 ℃, finds that solution at one group of new absorption peak of 325nm place appearance, then is F
-Anion solutions.
Embodiment 8, be acceptor, utilize the method for hydrogen nuclear magnetic resonance spectrum discrimination fluorion: in the nuclear-magnetism pipe, add 1.0 * 10 of acceptor 3a with m-benzenedicarbonyl thioureas derivative 3a
-2Mol * L
-1DMSO-d
6Solution is surveyed its proton nmr spectra, adds isopyknic object F then in the nuclear-magnetism pipe respectively
-, Cl
-, Br
-, I
-4-butyl ammonium 1.0 * 10
-2Mol * L
-1DMSO-d
6Solution is measured its proton nmr spectra respectively in 25 ℃; If the NH chemical shift of proton of acceptor molecule disappears, and then is F
-Negatively charged ion.
Embodiment 9, be acceptor, utilize the method for hydrogen nuclear magnetic resonance spectrum discrimination fluorion: in the nuclear-magnetism pipe, add 1.0 * 10 of acceptor 3b with m-benzenedicarbonyl thioureas derivative 3b
-2Mol * L
-1DMSO-d
6Solution is surveyed its proton nmr spectra, adds isopyknic object F then in the nuclear-magnetism pipe respectively
-, Cl
-, Br
-, I
-4-butyl ammonium 1.0 * 10
-2Mol * L
-1DMSO-d
6Solution is measured its proton nmr spectra respectively in 25 ℃; If the NH chemical shift of proton of acceptor molecule disappears, and then is F
-Negatively charged ion.
Embodiment 10, be acceptor, utilize the method for hydrogen nuclear magnetic resonance spectrum discrimination fluorion: in the nuclear-magnetism pipe, add 1.0 * 10 of acceptor 3c with m-benzenedicarbonyl thioureas derivative 3c
-2Mol * L
-1DMSO-d
6Solution is surveyed its proton nmr spectra, adds isopyknic object F then in the nuclear-magnetism pipe respectively
-, Cl
-, Br
-, I
-4-butyl ammonium 1.0 * 10
-2Mol * L
-1DMSO-d
6Solution is measured its proton nmr spectra respectively in 25 ℃; If the NH chemical shift of proton of acceptor molecule disappears, and then is F
-Negatively charged ion.
Claims (10)
1, a kind of m-benzenedicarbonyl thioureas derivative: its molecular structural formula is shown below:
R=NO wherein
2, be m-benzenedicarbonyl thioureas derivative 3a;
R=H is m-benzenedicarbonyl thioureas derivative 3b;
R=OC
2H
5, be m-benzenedicarbonyl thioureas derivative 3c.
2, the preparation method of a kind of m-benzenedicarbonyl thioureas derivative 3a of the present invention, 3b, 3c: be that m-phthaloyl chloride and the ammonium thiocyanate mol ratio with 1: 2.5～1: 3 is joined in the mortar, under the condition of phase-transfer catalyst, griding reaction 5～7 hours intermittently under room temperature obtains the isophthaloyl lsothiocyanates; The substituted aromatic amines that adds 2～2.5 times of m-phthaloyl chloride amount of substances again, griding reaction 6～48 hours intermittently under room temperature obtains yellow or flaxen precipitation; Filter, wash, and with the organic solvent recrystallization promptly; Its synthetic route is as follows:
R=NO wherein
2, be m-benzenedicarbonyl thioureas derivative 3a;
R=H is m-benzenedicarbonyl thioureas derivative 3b;
R=OC
2H
5, be m-benzenedicarbonyl thioureas derivative 3c.
3, as the preparation method of m-benzenedicarbonyl thioureas derivative 3a, 3b, 3c as described in the claim 2, it is characterized in that: described phase-transfer catalyst is a polyoxyethylene glycol-400, and its add-on is 2～4% of an ammonium thiocyanate amount of substance.
4, as the preparation method of m-benzenedicarbonyl thioureas derivative 3a, 3b, 3c as described in the claim 2, it is characterized in that: described organic solvent is DMF-C
2H
5OH-H
2O mixed solvent, wherein DMF: C
2H
5OH: H
2The mol ratio of O is 1: 0.8: 0.4～1: 1.2: 0.6.
5, m-benzenedicarbonyl thioureas derivative 3a, 3b, 3c are as the fluorion identification receptor.
6, the method as m-benzenedicarbonyl thioureas derivative 3a acceptor identification fluorion as described in the claim 5 is: pipette 2 * 10 of 1mL 3a acceptor respectively
-4Mol * L
-1DMSO solution adds 1mL F respectively in a series of 10mL colorimetric cylinders
-, Cl
-, Br
-, I
-0.01mol * the L of anionic 4-butyl ammonium
-1DMSO solution is diluted to scale with DMSO, and the concentration that makes the 3a acceptor is 2 * 10
-5Mol * L
-1, and various anion concentration is 50 times of the 3a acceptor density, mixes the back and observes colour-change, if solution colour becomes yellow, then is F
-Anion solutions.
7, the method as m-benzenedicarbonyl thioureas derivative 3a acceptor identification fluorion as described in the claim 5 is: pipette 2 * 10 of 1mL3a acceptor respectively
-4Mol * L
-1DMSO solution adds 1mL F respectively in a series of 10mL colorimetric cylinders
-, Cl
-, Br
-, I
-0.01mol * the L of anionic 4-butyl ammonium
-1DMSO solution is diluted to scale with DMSO, and the concentration that makes the 3a acceptor is 2 * 10
-5Mol * L
-1, and various anion concentration is 50 times of the 3a acceptor density, mixes, and surveys its uv-visible absorption spectras in 25 ℃, if find that solution at one group of new absorption peak of 417nm place appearance, then is the F-anion solutions.
8, the method as m-benzenedicarbonyl thioureas derivative 3b acceptor identification fluorion as described in the claim 5 is: pipette 2 * 10 of 1mL3b acceptor respectively
-4Mol * L
-1DMSO solution is in a series of 10mL colorimetric cylinders; Add 1mL F respectively
-, Cl
-, Br
-, I
-0.01mol * the L of anionic 4-butyl ammonium
-1DMSO solution is diluted to scale with DMSO, and the concentration that makes acceptor 3b is 2 * 10
-5Mol * L
-1, and various anion concentration is 50 times of the 3b acceptor density, mixes, and surveys its uv-visible absorption spectras in 25 ℃, if find that solution at one group of new absorption peak of 321nm place appearance, then is the F-anion solutions.
9, the method as m-benzenedicarbonyl thioureas derivative 3b acceptor identification fluorion as described in the claim 5 is: pipette 2 * 10 of 1mL acceptor 3c respectively
-4Mol * L
-1DMSO solution is in a series of 10mL colorimetric cylinders; Add 1mL F respectively
-, Cl
-, Br
-, I
-0.01mol * the L of anionic 4-butyl ammonium
-1DMSO solution is diluted to scale with DMSO, and the concentration that makes acceptor 3c is 2 * 10
-5Mol * L
-1, and various anion concentration is 50 times of the 3b acceptor density, mixes, and surveys its ultraviolet-visible absorption spectra in 25 ℃, finds that solution at one group of new absorption peak of 325nm place appearance, then is F
-Anion solutions.
10, the method as m-benzenedicarbonyl thioureas derivative 3a as described in the claim 5 or 3b or 3c acceptor identification fluorion is: add 1.0 * 10 of acceptor 3a or 3b or 3c in the nuclear-magnetism pipe
-2Mol * L
-1DMSO-d
6Solution is surveyed its proton nmr spectra, adds isopyknic object F then in the nuclear-magnetism pipe
-, Cl
-, Br
-, I
-The 1.0 * 10-2mol * L of 4-butyl ammonium
-1DMSO-d6 solution is measured its proton nmr spectra respectively in 25 ℃; If the NH chemical shift of proton of acceptor molecule disappears, and then is F
-Negatively charged ion.
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| CN102040547A (en) * | 2010-10-22 | 2011-05-04 | 西北师范大学 | Salicyl thiourea derivative, preparation method and application |
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| CN101417961B (en) * | 2008-12-06 | 2012-07-25 | 西北师范大学 | Anion receptor based on nitro phenylhydrazone and phenolic hydroxyl and preparation of anion test paper and use thereof |
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| CN101417989B (en) * | 2008-12-06 | 2011-05-11 | 西北师范大学 | Anion receptor based on nitrofuran formyl hydrazone and phenolic hydroxyl and preparation and use of organagel thereof |
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| CN102040547A (en) * | 2010-10-22 | 2011-05-04 | 西北师范大学 | Salicyl thiourea derivative, preparation method and application |
| CN102040547B (en) * | 2010-10-22 | 2013-07-10 | 西北师范大学 | Salicyl thiourea derivative, preparation method and application |
| CN102207455A (en) * | 2011-04-02 | 2011-10-05 | 朱丽君 | An open hole identification method for anions F -, ac - and H2PO4- |
| CN102207455B (en) * | 2011-04-02 | 2013-08-14 | 朱丽君 | An open hole identification method for anions F -, ac - and H2PO4- |
| CN110483572A (en) * | 2019-07-31 | 2019-11-22 | 广州钰芯传感科技有限公司 | A kind of three core gold alkynyl urea complexs and preparation method thereof with tetrahedral oxo-anions identification function |
| CN110483572B (en) * | 2019-07-31 | 2022-04-12 | 广州钰芯传感科技有限公司 | Trinuclear gold alkynyl urea complex with tetrahedral oxyanion recognition function and preparation method thereof |
| CN111103249A (en) * | 2019-12-30 | 2020-05-05 | 南阳师范学院 | Bis-thiourea anion recognition receptor and preparation method thereof |
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